Primer Remanufacturing – Red Phosphorus Mixtures

This testing sequence will be focused on an old Primer Mixture from the 1940’s using Red Phosphorus. The mixture was derived from a 1944 Paper on Primers entitled Primers for Small Arms Cartridges by M. J. ALBERT and H. F. OELBERG. The paper was transcribed into a digital .pdf format by Marshall Thompson and copyrighted in 2017. A copy of the multi-page paper can be found at:

https://www.aardvarkreloading.com/re...%20Oelberg.pdf

Red Phosphorus was explored by the US Government as a primer mixture, and actually used in 1949 as the “P-4 Formula. https://www.bevfitchett.us/chemical-...positions.html

About 1949 Frankford Arsenal manufactured an unusual priming mixture known as the P-4 primer (coded FA675):

Stabilized red phosphorus 18% Barium nitrate 82%

Although this was a simple, relatively safe mixture, and was a satisfactory primer, it was discontinued after a very short period because of two major disadvantages. It was shown that copper, bismuth, silver, iron, and nickel increased the oxidation rate of red phosphorus to acidic compounds. Primer cups had to be zinc plated to prevent contact with copper. The red phosphorus had to be of high purity, and it was necessary to remove the major impurities (iron and copper) from commercial red phosphorus before use, and to coat the purified material with up to 7.5% aluminum hydroxide which inhibited oxidation.

Although the P-4 primer was only in use for approximately 1 year, it was further improved in 1961 by coating the stabilized red phosphorus with PETN, RDX (cyclotrimethylenetrinitramine), or TNT giving the following primer mix:

Stabilized red phosphorus 25%

However, red phosphorus primers never achieved widespread use, presumably due to manufacturing difficulties.

Of interest is that the use of Red Phosphorus was recently resurrected as a potential “GREEN PRIMER”. The company ATK put out a Paper/Slide show on using Red Phosphorus as a key component in US Primers entitled: Non-toxic Heavy Metal Free Primers for Small Arms Cartridges – Red Phosphorous Based. Introducing ATK Lake City’s P4rimerTM .

https://ndiastorage.blob.core.usgovc...usky_520pm.pdf

The use of Red Phosphorus in home Remanufacturing of Primers has the same handicap of many formulas in that some components are difficult to acquire. I was able to acquire 200 grams (about ½ pound) for making primers after a 3 month search/wait.

The first test will be with the mixture derived from Chapter One of the Paper Primers for Small Arms Cartridges.


The formula used is a “Volume” ratio. The paper called out using an empty 22 LR case as the Measuring device.

Lead Nitrate 20%
Aluminum 20%
Red Phosphorus 20%
Barium Nitrate 40%

I wanted to measure by weight instead of volume – so I weighed a 22LR case filled full for of each of the chemicals and established the following Weights in Grains for the Mixture. This represents One Batch of Mixture.

Lead Nitrate 14.1 grains
Aluminum 0.9 grains
Red Phosphorus 2.7 grains
Barium Nitrate 14.8 grains
Total 32.5 grains

The filling & compacting from the reference called for filling the primer cup, packing with a wooden match, refilling and placing a paper foil on top followed by a primer anvil. I wanted to follow the processes I previously used in my other postings on Primer Remanufacturing since I had established personal success and reliability. I selected 10 Brass Primer Cups and sized them in the NOE Large Primer sizing die (cups have been reused 5 to 10 times each). I filled each cup using the mixture above; leveled at the top of the cup. I placed a Paper Disk foil cut from Cash register tape using a ¼ inch hole punch on top of the filled cups; and then compressed the disk/primer mixture on each primer using the same technique described in post #27 of my thread:

https://castboolits.gunloads.com/sho...readings/page2

The original description called for a “Dry Mix”; but I have found these to be problematic as some primer mixture seems to find a way to leak out of the cups when handled. I wanted to see if a “Wet Mix” could be used with this mixture so I loaded 5 rounds with a “Dry Mix”; and I used a 20:1 mixture of Alcohol and Varnish to wet the Foil & Primer Mixture underneath for 5 primers – let dry for 24 hours. All 10 primers were loaded as follows; but the Wet Primers are identified with a Red Marker to allow assessing performance of each process.

Load Data to be used in the Test will be:

Red Phosphorus mixture #1. Individual Large primer cups use ~ 0.55 grains for each primer cup.


Rifle: Remington 700 ADL Varmint .308
Barrel Twist: 1 in 12
Boolit: NOE 311041
Ballistic Coefficient: .220
Brinnel Hardness: 20
Bullet sized: .310
Alloy: 96% Lead, 3% Antimony, 1% Tin
Bullet Lube: Powder Coated with Eastwood Blue Paint.
Gas Check: Ameri-max Aluminum 0.14”
Powder: BLC-2 – 32 Grains with Dacron Over Powder
Primer: Remanufactured – Red Phosphorus Primer Mixture #1
Case: Mixed military and commercial Brass
OAL: 2.585 inches
Distance: 100 Yards.


Pictures of groups will be published after I test fire these primers.

Is this a "non-corrosive" mixture?

Quote:

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Originally Posted by atfsux

Is this a "non-corrosive" mixture?

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Yes.

Got to the Range this morning to fire the 10 Test rounds developed. Five were dry primer mix "Packed Only" similar to original instructions. The other five were "Wet Mix" with a 20:1 ratio of alcohol (91% alcohol and 9 % water from Walmart) and Varnish from Home Depot. Unfortunately I forgot to bring the tripod with me so I was unable to get a Chronograph reading as I originally intended.

Dry Mix for Red Phosphorus (Mixture from Chapter II) test target:

Attachment 317181
Group Size at 100yards was 4 & 3/8 inches (4 & 3/8 tall by 2 & 1/4 inc wide)


Attachment 317182
And; the Wet Mix Red Phosphorus (Mixture from Chapter II) Test Target:
Group Size at 100 Yards was 2 & 5/8 inches (only 1/2 inch tall, but 2 & 5/8 inches wide).


My original concern (not being a chemist) was that I might contaminate the primer mixture or have a reaction using the 20:1 wetting mixture. This is apparently not an issue with this chemical make up. In fact; the wet mix on a limited sample ( 5 shots and 5 shots); is exhibiting a significantly smaller group on paper. I am currently attributing that to the Primer Mixture being hardened into a single pellet with the mixture - keeping the mixture all in the cup and providing a harder surface for the Reaction when the firing pin and Anvil crush the pellet.

I will be looking at some other Adaptations of Red Phosphorus in the Primer Mixture in the next few weeks/months. Later this weekend I will attempt to break down the fired primers and see if there is anything to see in the residue. The brass was cleaner after firing or this Primer Mixture compared to many of the H048 and FH-42 Tests I have conducted; but there was powder fouling on the mouth, and some slight fouling on the sides of the cae.

Any idea of the shelf life of this type primer ?

Thanks , Jack

There are brief comments in historical articles that the Red Phosphorus Primer mix of 1949 were found to over time form an acidic reaction that attacked the brass Primer Cups. The solution at that time was to plate the Primer Cups in Zink.

Once again; I am not a Chemist - but I am personally thinking of using the "Silver" colored primer cups I have (salvaged from CCI primers such as the CC-34) in this application if it pans out. I believe the CCI are Chrome Plated - which I believe will resist any corrosion in long term storage.

I have run across a few citations that over the last 10 or so years there are patents and research ongoing to resurrect the Red Phosphorus containing primer mixtures because they are "Green" based on the individual chemicals and how they appear naturally in nature.

When it comes to the "Shelf Life" of primers - we can deduce that the H-48 and FH-42 mixtures have long shelf lives as Surplus Ammunition form the 1930's (and further back?) are still viable. The chemical make up is different than the Red Phosphorus primers of old and my mix testing - so we may have to try it (storing red Phosphorus containing primers) and see over time; or someone reading the thread and having made Red Phosphorus containing primers may be able to weigh in.

Just based on "looks" I think that the plating on the CCI cups is nickel similar to how some ammo is made with nickel plated brass.

I agree that using plated cups is a "good try" but I see that nickel is one of the "problem" metals listed in the OP

If the compound works good for short term use, longer term acceptability may be improved with zinc plating. This is not out of reach for a hobby activity.

The sealant you used may be useful to "dip paint" the insides of the cup. A very thin coating of varnish will certainly not hurt anything and may help separate the phosphorus and copper.

An alternate coating to try could be powder coat. Do the ASBB shake & bake, then wipe off all exterior powder before baking.

Lead styphnate and lead azide (the 2 primary priming compounds of the last century) are both sensitive to static electricity. Any word on red phosphorous being likewise?

The current flavor by the USofA Government Contractors exploring primers containing Red Phosphorus supposedly use an "Encapsulating" Chemical with the Red Phosphorus (prior to mixing the Red Phosphorus with other Chemicals for the Primer Mixture). Many of these techniques are probably beyond the capabilities of WE "Hobbyists".


Note: The primer mixture in Test Mix #1 (post #2 above) contains Lead Nitrate (a poisonous substance). So it would not fit the category of "Green". Test Mix #2 will contain Antimony Sulfide - instead of Lead Nitrate. Antimony is considered poisonous if ingested (said to resemble arsenic poisoning) - yet Antimony Sulfide has historically been used in medicinal and beauty preparations. Not sure how the purveyors/interpreters of "ALL THINGS GREEN" would rate the Test Mix #2 on the Green Scale.

I'll continue my explorations and report results. As we get more "Mature" we need things to keep our minds active and engaged - for me this is one of several I pursue to do that.

Ive had read several posts about using cap gun stripes to make primers. Nothing other than Potassium chlorate and red phosphorus Also known as a death mix. Please be careful out there! If your bent to do it use a wetting agent when mixing. Nitro cellulose is a good wetting agent when acetone is introduced

Quote:

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Originally Posted by super6

Ive had read several posts about using cap gun stripes to make primers. Nothing other than Potassium chlorate and red phosphorus Also known as a death mix. Please be careful out there! If your bent to do it use a wetting agent when mixing. Nitro cellulose is a good wetting agent when acetone is introduced

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This is touching on my plans for testing my mixture #3 downstream. It is known historically as "Armstong's Mixture". Still used in toy caps, fireworks, and other initiator requirements.

Only one time Have I made the Red Phosphorous KClO3 mix I do have scars to show for it my stupidity, it was way back in 1974 .
I am not trying to make primers for cartridge guns but have been tinkering with percussion caps. The original mix was Charcoal, KClO3 , Sulphur and gum Arabic as binder it must be done WET! I figure Barium Chlorate would be much less corrosive and am going to give it a try . A small amount of Aluminum powder may also help but can not be used with water .

I have tried Ammonium Perchlorate but it is not sensitive enough , when it does go off it is very powerful ! I tried it in several mixes it seemed noncorrosive unless sulfur was in mix . Some of the priming pellets used Nitrocellulose / acetone as a binder .

Have you tried using thinned Nitrocellulose lacquer as a binder?

After Post # 5 above; I went to the range again for testing. Those Primers using the Phosphorus mix #1 (P4-1) and Phosphorus Mix #2 (P4-2) were prepared and primer cups loaded when it was high humidity and raining. Results were very poor with groups in the 10 to 12 inch range at 100 yards and there were Fail to Fires with both mixtures. I pursued the use of a Nitro Cellulose liquid binder for the next testing (see post at: https://castboolits.gunloads.com/sho...ing&highlight= )


The P4-1 Mixture with an Acetone/NC (Nitro Cellulose) binder -single drop on mixture covered with a Paper Foil disk and then primer anvil - yielded this group at 100 yards. Load was an NOE 311041 powder coated boolit over a 30 Grain BLC-2 Powder charge and a Dacron tuft over the powder. Only 9 rounds. Group size was 3.5 Inches.
Avg: 1844 fps
High: 1900 fps
Low: 1741 fps
Standard Deviation: 48.9


Attachment 317484


The P4-2 Mixture with an Acetone/NC (Nitro Cellulose) binder -single drop on mixture covered with a Paper Foil disk and then primer anvil - yielded this group at 100 yards. Load was an RCBS 200 Silhouette powder coated boolit over a 30 Grain BLC-2 Powder charge and a Dacron tuft over the powder. 10 rounds. Group size was 2.25 Inches.
Avg: 1832 fps
High: 1885 fps
Low: 1762 fps
Standard Deviation: 45.7

Attachment 317485


I have been using “Left Overs” during these primer testing efforts. The NOE 311041 boolit does not perform as well in my Rem-700 308 Winchester rifle as does the RCBS 200 Silhouette boolit; so the comparison of groups may be flawed – primary objective is to explore the Primer Remanufacturing and any emerging issues (Such as the humidity causing problems).

I plan to shoot some more test sequences with the RCBS 200 Sil boolit; and using the Acetone/NC liquid binder this weekend or next week as we have Rain and Humidity again which will hopefully assist in determining if the Acetone/NC binder inhibits moisture issues for P4-1 and P4-2 mixtures compared to the Alcohol/Shellac mixture I used in Prima-All, H-48, and FH-42 primer mixtures. I will also back track to other posts on those mixtures and validate the Alcohol/Shellac mixture does not have problems for them in humidity and rain when preparing.

Have not been able to get to the range last week or so (Hay Hauling and Firewood Collection Ongoing). I did want to give those following this thread a cost overview estimate for materials on the two P4 primer types I have been evaluating. (Red Phosphorus based) Each of the two types has 4 chemicals, with the original reference citing in a Volumetric measurement. I converted those volumes to weights; which is what appears in my postings.

The following is a breakdown of costs based on the "BATCH" measurements. I utilized not only the retail cost of the chemical material; but also added the shipping costs and Hazmat Costs if required into the total cost. Then converted these to cost per GRAIN of chemical.



Attachment 318001

The Red Phosphorus and the Lead Nitrate are pretty pricy (both the material and the shipping); but in the amounts used it's not to bad compared to todays retail cost of primers.

The price for chemicals in the Test Mixture #1 runs about $1.15 for 100 primers.
The price for chemicals in the Test Mixture #2 runs about $0.85 for 100 Primers.

When I bought my primer chemicals; both the chemicals and shipping were lower than what I calculated using current on-line pricing. If our supply chains and shipping costs (Inflation) remains fairly stable - then the costs cited above should be valid in the future. Two pounds of Barrium Nitrate, and one pound each for the other chemicals (or 500 grams in some cases) shipped will need and investment of a couple hundred dollars - but will make MANY THOUSANDS OF PRIMERS.

P4-3

I was experiencing “Failure to Fire” on the P4 – 1 Primer Mixture. (Based on Red Phosphorus). This occurred during High Humidity periods and attempts to use a 20:1 Alcohol to Shellac or Varnish might help. The use of that mixture as a “Binder” did not resolve the issue.

I noted that some of the 350 Mesh Aluminum Powder I had was coming out of the mixture when the Liquid “Binder” was applied. This is a very small particulate Aluminum Powder, and will literally have some of it suspend in the air if one does not handle it carefully. I postulated that I needed to try something “Different”; so after some contemplation I hit on the concept of using “Tannerite” in the mix as a substitute for the 350 Mesh Aluminum powder I was previously using. I had bought a ½ pound Tannerite kit last year. Tannerite when mixed is 95% Ammonium Nitrate, and 5% Aluminum Powder.

The Ratio by weight in grains I came up for what I am calling my P4-3 Mixture is:

Lead Nitrate 14.1 grains
Tannerite 0.9 grains
Red Phosphorus 2.7 grains
Barium Nitrate 14.8 grains
Total 32.5 grains

The Ammonium Nitrate is in little round balls called “Prills” . I had to grind these into a fine powder. The Aluminum I used was from a 350 mesh 1 pound bag that I had bought last year. I mixed 28.5 grains of the finally ground Ammonium Nitrate Prills with 1.5 grains of the 350 Mesh aluminum. Mixing until it was a well mixed blend; and stored the 30 grains of Tannerite in a plastic pill box. I take 0.9 grains of the Tannerite from this Pill Box mixture each time I make 32.5 Grains of the P4-3 Mixture above.

I have fired about 50 of these primers made with the P4-3 Mixture. There were no Fail to Fires or Hang Fires in the tests. These test were in a Remington 700 .308 Winchester with a heavy 26 Inch Varmint Barrel. Primers only in these tests. The primer sound was strong and sharp, and the flames were very energetic – with very bright flashes on each ignition of 6 to 8 inches from the end of the barrel. These mixtures and testing were all performed in High Humidity conditions as we have been having rain every day over the last week or so.

This mixture Seems to be performing well. I am concerned about the Ammonium Nitrate and it’s potential corrosive impact if the firearm is not cleaned adequately; but it does provide a solution if required.

Note:

This week I finally received an order of 75 Mesh Aluminum Powder I had been searching for over the last 4 months. Some of the Work on Aardvark Reloading and other sources cite that too fine an Aluminum Powder may not provide consistent ignition. I am/have been speculating that perhaps the Fail to Fires I experienced were not Humidity related – but the Aluminum Powder mesh size I have been using. I will do additional Work with the P-1 Mixture using the 75 Mesh Aluminum Powder in the next few weeks once I shake the Persistent Cough I currently have.

I am hoping the 75 Mesh Aluminum Powder will resolve the issue; as that will put my P4-1 formula back as my primary choice – based on it’s being Non-Corrosive and very clean when fired.

I fired 9 Test Rounds today. The Primers what I am calling the P4-3 Formula; as listed in Post #16 above. The load data was:

Rifle: Remington 700 ADL Varmint .308
Barrel Twist: 1 in 12
Wind: 7 Mph left to right.
Temp: 37 degrees F.
Boolit: 308 RCBS 200 Silhouette
Ballistic Coefficient: 0.255
Brinell Hardness: 20
Bullet sized: .310
Alloy: 96% Lead, 3% Antimony, 1% Tin
Bullet Powder Coated: Powder Coated with Eastwood Blue Paint.
Gas Check: Ameri-max Aluminum 0.14”
Powder: BLC-2 30 Grains with a Dacron Filler
Primer: Remanufactured Remington 9 1/2 primer cup - Red Phosphorus P3 Primer Mixture
Case: Mixed Brass
OAL: 1.8 inches
Distance: 100 Yards.


Target Pic:
Attachment 320078

I am going to reshoot this mixture. After each shot I had "Smoke" curling from the Chamber/Bolt area after firing each round. Coming from the Primer/Case after the pressure built, expelled the boolit, and powder has burned? Interesting observation - will have to see if it repeats. Additionally, I will be depriming the cups from the Brass and evaluating them this weekend.

As always, very interesting, sir!

Quote:

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Originally Posted by MUSTANG

I fired 9 Test Rounds today. The Primers what I am calling the P3 Formula; as listed in Post #16 above.

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Post #16 lists a mixture called P4-3...... Is it called P3 now?

Changed the verbiage to P4-3 s it should have been. Thanks.

I posted some time ago I have been trying without a lot of luck making Percussion caps using Barium Chlorate rather then Potassium chlorate I read a few articles about red Phosphorous and can not find a place to get it because of it's use in meth production?

Some of my reading also hit on using larger grains of fuel to get better firing success .

Here is a quote from link below you may find interesting :
With these facts in mind, we have developed 85 a noncorrosive priming composition which, like the potassium chlorate primer, contains only fuels and oxidizers that are nonexplosive in themselves. The sensitiveness of this priming composition depends on the use of red phosphorous. As a specific example, we have found the following mixture suitable for small arms primers: Percent Red phosphorous----------------------- 25 Barium nitrate-------------------- - .58 Antimony sulfide...--------------------- 17 This mixture may be blended and loaded into primer cups in the usual way. It has been found advantageous to use a small amount of glue or 50 gum as a binder for the pellet.

From:
https://www.freepatentsonline.com/2194480.html

Quote:

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Originally Posted by MUSTANG

When it comes to the "Shelf Life" of primers - we can deduce that the H-48 and FH-42 mixtures have long shelf lives as Surplus Ammunition form the 1930's (and further back?) are still viable.

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According to Hatcher’s Notebook, the U.S. began using the FA-70 primer compound during WW1 because of misfires from the H-48 and FH-42 primers. The misfire problem was traced to excessive humidity causing sulfur and KClO3 to interact, forming sulfuric acid which degraded the primers.

FA-70 essentially replaced the sulfur with Lead Thiocyanate (AKA Lead Sulphocyanate), and added a pinch of TNT -

Potassium Chlorate………………….53
Antimony Sulfide……….…………...17
Lead Thiocyanate………………...…25
TNT………………….........……………….5

A bit off topic but has to do with old primers A friend mail ordered a 6.5 Mannlicher carbine just before GCA 68 took effect ,he paid the postman for the gun and a large box of ammo at 10 years old . A lot of that corrosive ammo would hangfire or misfire when we pulled the bullets the powder was ruined . We pulled some bullets dumped the powder and fired the primers they either made a pop , a slow sizzling sound or sizzled and popped loudly . We assumed the latter would have been a hangfire . When this ammo did go off right it shot well and sent that 160 grain long round nose bullet down range accurately . It also showed how badly a shooter flinched!